Aromatic vinyl copolymer and thermoplastic resin composition including the same

ABSTRACT

An aromatic vinyl copolymer is a polymer of a reaction mixture including: an aromatic vinyl compound; a vinyl cyanide compound; a first silicone compound having a weight average molecular weight of about 150 g/mol to less than about 6,000 g/mol and including at least two unsaturated reactive groups; and a second silicone compound having a weight average molecular weight of about 6,000 g/mol to about 100,000 g/mol and including at least two unsaturated reactive groups. A thermoplastic resin composition including the aromatic vinyl copolymer can exhibit excellent matting properties, impact resistance, and balance therebetween.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims priority under 35 USC Section 119 to and thebenefit of Korean Patent Application 10-2014-0132666, filed Oct. 1,2014, the entire disclosure of which is incorporated herein byreference.

FIELD

The present invention relates to an aromatic vinyl copolymer, athermoplastic resin composition including the same, and a molded articleformed of the thermoplastic resin composition.

BACKGROUND

Thermoplastic resins exhibit excellent physical properties, such as lowspecific gravity, good moldability, and good impact resistance, ascompared with glass or metal, and are useful for housings ofelectrical/electronic products, automotive interior/exterior materials,and exterior materials for construction. Particularly, with the trend ofproducing larger and lighter weight electrical/electronic products,plastic products made of thermoplastic resins are quickly replacingexisting glass or metal-based products.

Moreover, for environmental friendliness and process cost reduction,there is an increasing need for non-painted materials which can exhibitappearance and surface properties such as color and gloss withoutadditional processes. In particular, for applications such asinterior/exterior materials of automobiles and electronics, exteriormaterials for buildings, and the like, there is a need for developmentof low-gloss products which satisfy consumer demand for a luxuriousappearance.

To reduce surface gloss of a molded article (interior/exterior materialsand the like) formed of a thermoplastic resin composition without apost-painting process, a process of increasing the size of rubber in theresin composition to several micrometers or more, or a process ofincorporating highly crosslinked matting agents and/or inorganic mattingagents such as talc into the resin composition may be employed. When therubber in the resin composition has a large size, the resin compositioncan have excellent extinction efficiency or surface uniformity. In thiscase, however, the resin composition can exhibit deterioration in impactresistance as compared with resin compositions which include rubbershaving a relatively small size in the same parts by weight. In addition,a thermoplastic resin composition including a highly crosslinkablematting agent and/or an inorganic matting agent can also exhibitdeterioration in impact resistance and poor appearance properties due todeterioration in surface uniformity thereof.

Therefore, there is a need for a thermoplastic resin composition whichexhibits excellent matting properties, impact resistance, and balancetherebetween with minimal or no deterioration in appearance thereof dueto a matting agent and the like.

SUMMARY OF THE INVENTION

Embodiments provide an aromatic vinyl copolymer which can have excellentmatting properties and impact resistance, a thermoplastic resincomposition that can exhibit excellent matting properties, impactresistance, and balance therebetween by use of the aromatic vinylcopolymer, and a molded article formed of the thermoplastic resincomposition.

The aromatic vinyl copolymer is a polymer of a reaction mixture whichincludes: an aromatic vinyl compound; a vinyl cyanide compound; a firstsilicone compound having a weight average molecular weight of about 150g/mol to less than about 6,000 g/mol and including at least twounsaturated reactive groups; and a second silicone compound having aweight average molecular weight of about 6,000 g/mol to about 100,000g/mol and including at least two unsaturated reactive groups.

In exemplary embodiments, the aromatic vinyl copolymer may include about0.05 parts by weight to about 10 parts by weight of the first siliconecompound and about 0.05 parts by weight to about 10 parts by weight ofthe second silicone compound, each based on about 100 parts by weight ofa monomer mixture including about 60% by weight (wt %) to about 80 wt %of the aromatic vinyl compound and about 20 wt % to about 40 wt % of thevinyl cyanide compound.

In exemplary embodiments, the first silicone compound may be a compoundrepresented by Formula 1, and the second silicone compound may be acompound represented by Formula 2:

wherein a, b and c are the same or different and are each independentlyan integer of 0 to 79 (provided that a, b and c are not 0 at the sametime, and a+b+c ranges from 1 to 79); R₁ to R₈ are the same or differentand are each independently a hydrogen atom, a substituted orunsubstituted C₁ to C₃₀ alkyl group, a substituted or unsubstituted C₂to C₃₀ alkenyl group, a substituted or unsubstituted C₂ to C₃₀ alkynylgroup, a substituted or unsubstituted C₃ to C₃₀ cycloalkyl group, asubstituted or unsubstituted C₆ to C₃₀ aryl group, a substituted orunsubstituted C₁ to C₃₀ heteroaryl group, a (meth)acrylate group, ahydroxyl group, an alkoxy group, an amino group, an epoxy group, acarboxyl group, a halogen group, an ester group, an isocyanate group, ora mercapto group; with the proviso that at least two of R₁ to R₈ includepolymerizable unsaturated reactive groups; and the compound may have alinear structure or a cyclic structure in which R₁ and R₈ are linked toeach other or form a single bond;

wherein d, e and f are the same or different and are each independentlyan integer of 0 to 1,500 (provided that d, e and f are not 0 at the sametime, and d+e+f ranges from 80 to 1,500); R₉ to R₁₆ are the same ordifferent and are each independently a hydrogen atom, a substituted orunsubstituted C₁ to C₃₀ alkyl group, a substituted or unsubstituted C₂to C₃₀ alkenyl group, a substituted or unsubstituted C₂ to C₃₀ alkynylgroup, a substituted or unsubstituted C₃ to C₃₀ cycloalkyl group, asubstituted or unsubstituted C₆ to C₃₀ aryl group, a substituted orunsubstituted C₁ to C₃₀ heteroaryl group, a (meth)acrylate group, ahydroxyl group, an alkoxy group, an amino group, an epoxy group, acarboxyl group, a halogen group, an ester group, an isocyanate group, ora mercapto group; with the proviso that at least two of R₉ to R₁₆include polymerizable unsaturated reactive groups.

In exemplary embodiments, the compound represented by Formula 1 mayinclude a compound represented by Formula 3:

where R₁₇ to R₂₂ are the same or different and are each independently ahydrogen atom, a substituted or unsubstituted C₁ to C₂₀ alkyl group, asubstituted or unsubstituted C₂ to C₂₀ alkenyl group, or a substitutedor unsubstituted C₆ to C₂₀ aryl group; R₂₃ to R₂₅ are the same ordifferent and are each independently a hydrogen atom or a substituted orunsubstituted C₁ to C₆ alkyl group; and n is an integer of 1 to 6.

In exemplary embodiments, the first silicone compound may have a weightaverage molecular weight of about 150 g/mol to about 3,000 g/mol, andthe second silicone compound may have a weight average molecular weightof about 6,500 g/mol to about 30,000 g/mol.

In exemplary embodiments, a difference in weight average molecularweight between the first silicone compound and the second siliconecompound may range from about 5,000 g/mol to about 20,000 g/mol.

In exemplary embodiments, the reaction mixture may further include apolyfunctional vinyl compound including at least one of divinylbenzene,ethylene glycol di(meth)acrylate, allyl(meth)acrylate, diallylphthalate, diallyl malate, and triallyl isocyanurate.

In exemplary embodiments, the aromatic vinyl copolymer may include about5 wt % to about 100 wt % of insolubles remaining after Soxhletextraction for about 48 hours using tetrahydrofuran (THF) based on thetotal weight of the aromatic vinyl copolymer.

In exemplary embodiments, the aromatic vinyl copolymer may include about0.03 wt % to about 3.26 wt % of silicon as measured by X-rayfluorescence (XRF) analysis based on the total weight of the aromaticvinyl copolymer.

In exemplary embodiments, the aromatic vinyl copolymer may have a glasstransition temperature of about 95° C. to about 115° C.

Another embodiment relates to a thermoplastic resin composition. Thethermoplastic resin composition includes the aromatic vinyl copolymer asset forth above.

In exemplary embodiments, the thermoplastic resin composition mayinclude the aromatic vinyl copolymer in an amount of about 1 wt % toabout 50 wt % based on the total weight (100 wt %) of the thermoplasticresin composition.

In exemplary embodiments, the thermoplastic resin composition mayinclude a thermoplastic resin including at least one of arubber-modified aromatic copolymer, a polycarbonate resin, and apoly(meth)acrylate resin.

In exemplary embodiments, the thermoplastic resin composition may have:a gloss of about 20% to about 55% as measured at an angle of about 60°in accordance with ASTM D523; and an Izod impact strength of about 10kgf·cm/cm to about 30 kg·cm/cm as measured on an about ⅛″ thick specimenin accordance with ASTM D256.

Another embodiment relates to a molded article formed of thethermoplastic resin composition as set forth above.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a Soxhlet extractor according to one embodiment of thepresent invention.

DETAILED DESCRIPTION

Exemplary embodiments now will be described more fully hereinafter inthe following detailed description, in which some, but not allembodiments of the invention are described. Indeed, this invention maybe embodied in many different forms and should not be construed aslimited to the embodiments set forth herein; rather, these embodimentsare provided so that this disclosure will satisfy applicable legalrequirements.

In accordance with exemplary embodiments, an aromatic vinyl copolymer isa polymer of a reaction mixture which includes: (a) an aromatic vinylcompound; (B) a vinyl cyanide compound; (C) a first silicone compoundhaving a weight average molecular weight of about 150 g/mol to less thanabout 6,000 g/mol and including at least two unsaturated reactivegroups; and (D) a second silicone compound having a weight averagemolecular weight of about 6,000 g/mol to about 100,000 g/mol andincluding at least two unsaturated reactive groups.

(A) Aromatic Vinyl Compound

Examples of the aromatic vinyl compound may include without limitationstyrene, α-methylstyrene, β-methylstyrene, p-methylstyrene,p-t-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene,dichlorostyrene, dibromostyrene, vinylnaphthalene, and the like, andmixtures thereof. In exemplary embodiments, the aromatic vinyl compoundmay include styrene, α-methylstyrene, and/or a mixture thereof.

In exemplary embodiments, the aromatic vinyl compound may be present inan amount of about 60 wt % to about 80 wt %, for example, about 65 wt %to about 75 wt %, based on the total weight (100 wt %) of a monomermixture ((A)+(B)) including the (A) aromatic vinyl compound and the (B)vinyl cyanide compound. In some embodiments, the monomer mixture mayinclude the aromatic vinyl compound in an amount of about 60, 61, 62,63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, or80 wt %. Further, according to some embodiments, the amount of thearomatic vinyl compound can be in a range from about any of theforegoing amounts to about any other of the foregoing amounts.

Within this range, a thermoplastic resin composition including thearomatic vinyl copolymer can have excellent impact strength and heatresistance.

(B) Vinyl Cyanide Compound

Examples of the vinyl cyanide compound may include without limitationacrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile,α-chloroacrylonitrile, fumaronitrile, and the like, and mixturesthereof. In exemplary embodiments, the vinyl cyanide compound mayinclude acrylonitrile, methacrylonitrile, or the like.

In exemplary embodiments, the vinyl cyanide compound may be present inan amount of about 20 wt % to about 40 wt %, for example, about 25 wt %to about 35 wt %, based on the total weight (100 wt %) of the monomermixture ((A)+(B)) including the (A) aromatic vinyl compound and the (B)vinyl cyanide compound. In some embodiments, the monomer mixture mayinclude the vinyl cyanide compound in an amount of about 20, 21, 22, 23,24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, or 40 wt%. Further, according to some embodiments, the amount of the vinylcyanide compound can be in a range from about any of the foregoingamounts to about any other of the foregoing amounts.

Within this range, a thermoplastic resin composition including thearomatic vinyl copolymer can have excellent mechanical properties,moldability, and matting properties.

(C) First Silicone Compound

According to the present invention, the first silicone compound isprovided to realize excellent impact resistance and matting properties,has a weight average molecular weight of about 150 g/mol to less thanabout 6,000 g/mol as measured by gel permeation chromatography (GPC),and includes at least two unsaturated reactive groups.

In exemplary embodiments, the first silicone compound may be a compoundrepresented by Formula 1.

wherein a, b and c are the same or different and are each independentlyan integer of 0 to 79 (provided that a, b and c are not 0 at the sametime, and a+b+c ranges from 1 to 79); R₁ to R₈ are the same or differentand are each independently a hydrogen atom, a substituted orunsubstituted C₁ to C₃₀ alkyl group, a substituted or unsubstituted C₂to C₃₀ alkenyl group, a substituted or unsubstituted C₂ to C₃₀ alkynylgroup, a substituted or unsubstituted C₃ to C₃₀ cycloalkyl group, asubstituted or unsubstituted C₆ to C₃₀ aryl group, a substituted orunsubstituted C₁ to C₃₀ heteroaryl group, a (meth)acrylate group, ahydroxyl group, an alkoxy group, an amino group, an epoxy group, acarboxyl group, a halogen group, an ester group, an isocyanate group, ora mercapto group; with the proviso that at least two of R₁ to R₈ includepolymerizable unsaturated reactive groups.

The compound can have a linear or cyclic structure. For example, when R₁and R₈ are linked to each other or form a single bond, the compound maybe a cyclic compound represented by Formula 1a:

wherein a, b, c and R₂ to R₇ are defined as in Formula 1.

As used herein, unless otherwise stated, the term “substituted” meansthat a hydrogen atom is substituted with a substituent including ahalogen group, a C₁ to C₃₀ alkyl group, a C₁ to C₃₀ haloalkyl group, aC₆ to C₃₀ aryl group, a C₂ to C₃₀ heteroaryl group, a hydroxyl group, aC₁ to C₂₀ alkoxy group, a (meth)acrylate group, an amino group, an epoxygroup, a carboxyl group, an ester group, an isocyanate group, a mercaptogroup, and/or a combination thereof. As used herein, unless otherwisestated, the term “hetero” refers to at least one heteroatom such as N,O, S and/or P in a chemical formula.

In addition, the term “(meth)acryl” refers to “acryl” and/or“methacryl.” For example, the term “(meth)acrylates” refers to“acrylates” and/or “methacrylates.”

In exemplary embodiments, the compound represented by Formula 1 mayinclude a compound (cyclic structure) represented by Formula 3.

where R₁₇ to R₂₂ are the same or different and are each independently ahydrogen atom, a substituted or unsubstituted C₁ to C₂₀ alkyl group, asubstituted or unsubstituted to C₂₀ alkenyl group, or a substituted orunsubstituted C₆ to C₂₀ aryl group; R₂₃ to R₂₅ are the same or differentand are each independently a hydrogen atom or a substituted orunsubstituted C₁ to C₆ alkyl group; and n is an integer of 1 to 6.

Examples of the first silicone compound may include without limitation1,3,5-triisopropyl-1,3,5-trivinyl-cyclotrisiloxane,1,3,5,7-tetraisopropyl-1,3,5,7-tetravinyl-cyclotetrasiloxane,1,3,5,7,9-pentaisopropyl-1,3,5,7,9-pentavinyl-cyclopentasiloxane,1,3,5-tri-sec-butyl-1,3,5-trivinyl-cyclotrisiloxane,1,3,5,7-tetra-sec-butyl-1,3,5,7-tetravinyl-cyclotetrasiloxane,1,3,5,7,9-penta-sec-butyl-1,3,5,7,9-pentavinyl-cyclopentasiloxane,1,3,5-triisopropyl-1,3,5-trimethyl-cyclotrisiloxane,1,3,5,7-tetraisopropyl-1,3,5,7-tetramethyl-cyclotetrasiloxane,1,3,5,7,9-pentaisopropyl-1,3,5,7,9-pentamethyl-cyclopentasiloxane,1,3,5-triisopropyl-1,3,5-triethyl-cyclotrisiloxane,1,3,5,7-tetraisopropyl-1,3,5,7-tetraethyl-cyclotetrasiloxane,1,3,5,7,9-pentaisopropyl-1,3,5,7,9-pentaethyl-cyclopentasiloxane,1,1,3,3,5,5-hexaisopropyl-cyclotrisiloxane,1,1,3,3,5,5,7,7-octaisopropyl-cyclotetrasiloxane,1,1,3,3,5,5,7,7,9,9-decaisopropyl-cyclopentasiloxane,1,3,5-tri-sec-butyl-1,3,5-trimethyl-cyclotrisiloxane,1,3,5,7-tetra-sec-butyl-1,3,5,7-tetramethyl-cyclotetrasiloxane,1,3,5,7,9-penta-sec-butyl-1,3,5,7,9-pentamethyl-cyclopentasiloxane,1,3,5-tri-sec-butyl-1,3,5-triethyl-cyclotrisiloxane,1,3,5,7-tetra-sec-butyl-1,3,5,7-tetraethyl-cyclotetrasiloxane,1,3,5,7,9-penta-sec-butyl-1,3,5,7,9-pentaethyl-cyclopentasiloxane,1,3,5-triisopropyl-cyclotrisiloxane,1,3,5,7-tetraisopropyl-cyclotetrasiloxane,1,3,5,7,9-pentaisopropyl-cyclopentasiloxane,1,3,5-tri-sec-butyl-cyclotrisiloxane,1,3,5,7-tetra-sec-butyl-cyclotetrasiloxane,1,3,5,7,9-penta-sec-butyl-cyclopentasiloxane,1,3,5-trimethyl-1,3,5-trivinyl-cyclotrisiloxane,1,3,5,7-tetramethyl-1,3,5,7-tetravinyl-cyclotetrasiloxane,1,3,5,7,9-pentamethyl-1,3,5,7,9-pentavinyl-cyclopentasiloxane,1,3,5-triethyl-1,3,5-trivinyl-cyclotrisiloxane,1,3,5,7-tetraethyl-1,3,5,7-tetravinyl-cyclotetrasiloxane,1,3,5,7,9-pentaethyl-1,3,5,7,9-pentavinyl-cyclopentasiloxane, and thelike, and mixtures thereof.

The first silicone compound may be obtained by mixing divinylsilane,trivinylsilane, dimethyldivinylsilane, divinylmethylsilane,methyltrivinylsilane, diphenyldivinylsilane, divinylphenylsilane,trivinylphenylsilane, divinylmethylphenylsilane, tetravinylsilane,dimethylvinyldisiloxane, and/or divinyldiphenylchlorosilane, withoutbeing limited thereto.

In exemplary embodiments, the first silicone compound can include1,3,5-trimethyl-1,3,5-trivinyl-cyclotrisiloxane,1,3,5,7-tetramethyl-1,3,5,7-tetravinyl-cyclotetrasiloxane,1,3,5,7,9-pentamethyl-1,3,5,7,9-pentavinyl-cyclopentasiloxane,1,3,5-triethyl-1,3,5-trivinyl-cyclotrisiloxane,1,3,5,7-tetraethyl-1,3,5,7-tetravinyl-cyclotetrasiloxane,1,3,5,7,9-pentaethyl-1,3,5,7,9-pentavinyl-cyclopentasiloxane, and/or amixture thereof. For example, the first silicone compound can include1,3,5,7-tetramethyl-1,3,5,7-tetravinyl-cyclotetrasiloxane.

In exemplary embodiments, the first silicone compound may have a weightaverage molecular weight of about 150 g/mol to less than about 6,000g/mol, for example, about 150 g/mol to about 3,000 g/mol, and as anotherexample about 150 g/mol to about 1,000 g/mol. Within this range, thesilicone compound can allow easy control over the degree of crosslinkingof the copolymer and smooth crosslinking, and thereby can provideexcellent matting properties.

In exemplary embodiments, the first silicone compound may be present inan amount of about 0.05 parts by weight to about 10 parts by weight, forexample, about 0.5 parts by weight to about 5 parts by weight, based onabout 100 parts by weight of the monomer mixture ((A)+(B)) including the(A) aromatic vinyl compound and the (B) vinyl cyanide compound. In someembodiments, the monomer mixture may include the first silicone compoundin an amount of about 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.2, 0.3, 0.4,0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 parts byweight. Further, according to some embodiments, the amount of the firstsilicone compound can be in a range from about any of the foregoingamounts to about any other of the foregoing amounts.

Within this range, the silicone compound can allow easy control over thedegree of crosslinking of the copolymer, and thereby can provide uniformand excellent matting properties to the copolymer with minimal or nodeterioration in impact resistance, heat resistance and the like.

(D) Second Silicone Compound

The second silicone compound is used to provide excellent impactresistance and matting properties, has a weight average molecular weightof about 6,000 g/mol to about 100,000 g/mol as measured by gelpermeation chromatography (GPC), and includes at least two unsaturatedreactive groups.

In exemplary embodiments, the second silicone compound may be a compoundrepresented by Formula 2.

wherein d, e and f are the same or different and are each independentlyan integer of 0 to 1,500 (provided that d, e and f are not 0 at the sametime, and d+e+f ranges from 80 to 1,500); R₉ to R₁₆ are the same ordifferent and are each independently a hydrogen atom, a substituted orunsubstituted C₁ to C₃₀ alkyl group, a substituted or unsubstituted C₂to C₃₀ alkenyl group, a substituted or unsubstituted C₂ to C₃₀ alkynylgroup, a substituted or unsubstituted C₃ to C₃₀ cycloalkyl group, asubstituted or unsubstituted C₆ to C₃₀ aryl group, a substituted orunsubstituted C₁ to C₃₀ heteroaryl group, a (meth)acrylate group, ahydroxyl group, an alkoxy group, an amino group, an epoxy group, acarboxyl group, a halogen group, an ester group, an isocyanate group, ora mercapto group; with the proviso that at least two of R₉ to R₁₆include polymerizable unsaturated reactive groups.

In exemplary embodiments, examples of the compound represented byFormula 2 may include compounds represented by Formula 2a, without beinglimited thereto.

wherein each R₂₆ is independently a hydrogen atom or a C₁ to C₁₀ alkylgroup; each R₂₇ is independently a single bond or a C₁ to C₁₀ alkylenegroup; each R₂₈ is independently a vinyl group, a (meth)acrylate group,or an epoxy group; and m is an integer of 80 to 1,500.

For example, the compound represented by Formula 2a may be methacrylatedpolydimethylsiloxane (MPDMS, R₂₆: methyl group, R₂₇: propylene group,R₂₈: (meth)acrylate group) having a weight average molecular weight ofabout 6,000 g/mol to about 100,000 g/mol, without being limited thereto.

In exemplary embodiments, the second silicone compound may have a weightaverage molecular weight of about 6,000 g/mol to about 100,000 g/mol,for example, about 6,500 g/mol to about 30,000 g/mol, and as anotherexample about 7,000 g/mol to about 20,000 g/mol. Within this range, thesilicone compound can allow easy control over the degree of crosslinkingof the copolymer and smooth crosslinking, and can thereby provideexcellent matting properties.

In addition, a difference in weight average molecular weight between thefirst silicone compound and the second silicone compound may range fromabout 5,000 g/mol to about 20,000 g/mol, for example, from about 5,400g/mol to about 19,850 g/mol, and as another example from about 8,000g/mol to about 12,000 g/mol. Within this range, a thermoplastic resincomposition including the aromatic vinyl copolymer can have excellentimpact resistance and matting properties.

In exemplary embodiments, the second silicone compound may be present inan amount of about 0.05 parts by weight to about 10 parts by weight, forexample, about 0.5 parts by weight to about 5 parts by weight, based onabout 100 parts by weight of the monomer mixture ((A)+(B)) including the(A) aromatic vinyl compound and the (B) vinyl cyanide compound. In someembodiments, the monomer mixture may include the second siliconecompound in an amount of about 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.2,0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10parts by weight. Further, according to some embodiments, the amount ofthe second silicone compound can be in a range from about any of theforegoing amounts to about any other of the foregoing amounts.

Within this range, the silicone compound can allow easy control over thedegree of crosslinking of the copolymer, and can provide uniform andexcellent matting properties to the copolymer with minimal or nodeterioration in impact resistance, heat resistance, and the like.

In exemplary embodiments, a weight ratio of the first silicone compoundto the second silicone compound (first silicone compound:second siliconecompound) may range from about 1:0.1 to about 1:3, for example, fromabout 1:0.25 to about 1:1.5. Within this range, the silicone compoundcan allow easy control over the degree of crosslinking of the copolymer,and can provide excellent impact resistance and matting properties tothe copolymer.

According to the present invention, in the aromatic vinyl copolymer, thereaction mixture may further include a polyfunctional vinyl compoundincluding at least one of divinylbenzene, ethylene glycoldi(meth)acrylate, allyl(meth)acrylate, diallyl phthalate, diallyl malateand/or triallyl isocyanurate in order to control the degree ofcrosslinking and a polymerization rate of the copolymer.

In exemplary embodiments, the polyfunctional vinyl compound may bepresent in an amount of about 0.001 parts by weight to about 10 parts byweight, for example, about 0.01 parts by weight to about 3 parts byweight, based on about 100 parts by weight of the monomer mixture((A)+(B)) including the (A) aromatic vinyl compound and the (B) vinylcyanide compound. Within this range, it can be possible to easilycontrol the degree of crosslinking and polymerization rate of thecopolymer and to provide excellent matting properties with minimal or nodeterioration in impact resistance and heat resistance.

According to the present invention, the aromatic vinyl copolymer may beprepared by a typical polymerization method such as suspensionpolymerization, emulsion polymerization, and solution polymerization,without being limited thereto. For example, the aromatic vinyl copolymermay be prepared by suspension polymerization. In exemplary embodiments,a polymerization initiator and a chain transfer agent may be added tothe reaction mixture including the components in the amounts as setforth above to prepare a reaction mixture solution, followed bysuspension polymerization by introducing the reaction mixture solutioninto an aqueous solution in which a suspension stabilizer and the likeare dissolved, thereby preparing the aromatic vinyl copolymer. As usedhere, polymerization temperature and polymerization time can be suitablyadjusted. For example, polymerization may be performed at apolymerization temperature of about 65° C. to about 125° C., for exampleabout 70° C. to about 120° C., for about 1 to 8 hours.

The polymerization initiator may be any typical radical polymerizationinitiator known in the art. For example, the polymerization initiatormay include octanoyl peroxide, decanoyl peroxide, lauroyl peroxide,benzoyl peroxide, monochlorobenzoyl peroxide, dichlorobenzoyl peroxide,p-methylbenzoyl peroxide, tert-butyl perbenzoate,azobisisobutyronitrile, and/or azobis-(2,4-dimethyl)-valeronitrile,without being limited thereto. These polymerization initiators may beused alone or in combination thereof. The polymerization initiator maybe present in an amount of about 0.01 parts by weight to about 10 partsby weight, for example, about 0.03 parts by weight to about 5 parts byweight, based on about 100 parts by weight of the reaction mixture,without being limited thereto.

The chain-transfer agent may be used to control weight average molecularweight of the copolymer and enhance thermal stability of the copolymer.The chain transfer agent may include typical chain transfer agents knownin the art. Examples of the chain-transfer agent may include: alkylmercaptan in the form of CH₃(CH₂)_(n)SH (where n is an integer of 1 to20) including n-butyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan,t-dodecyl mercaptan, isopropyl mercaptan, and n-amyl mercaptan;halogenated compounds including carbon tetrachloride; and aromaticcompounds including α-methylstyrene dimers and α-ethylstyrene dimers,without being limited thereto. These may be used alone or in combinationthereof. The chain transfer agent may be present in an amount of about0.01 parts by weight to about 10 parts by weight, for example, about0.02 parts by weight to about 5 parts by weight, based on about 100parts by weight of the reaction mixture. Within this range, thecopolymer can have heat stability and appropriate molecular weight.

The aromatic vinyl copolymer may be polymerized by introducing thereaction mixture solution into an aqueous solution including at leastone or more additives, such as suspension stabilizers, suspensionstabilization aids, and/or antioxidants. The additive may be present inan amount of about 0.001 parts by weight to about 20 parts by weightbased on about 100 parts by weight of the reaction mixture, withoutbeing limited thereto.

Examples of the suspension stabilizer may include: organic suspensionstabilizers including homopolymers and/or copolymers of acrylic acidand/or methacrylic acid, polyalkyl acrylate-acrylic acid,polyolefin-maleic acid, polyvinyl alcohol, and cellulose; inorganicsuspension stabilizers including tricalcium phosphate; and the like, andmixtures thereof, without being limited thereto. As used herein, theacrylic acid or methacrylic acid may be in the form of a salt of sodium,potassium, or ammonium to ensure appropriate solubility.

Examples of the suspension stabilization aids may include disodiumhydrogen phosphate, sodium dihydrogen phosphate and the like, and mayalso include sodium sulfate in order to control solubility of awater-soluble polymer or monomer, without being limited thereto. Thesemay be used alone or in combination thereof.

Examples of the antioxidant may include octadecyl3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, triethyleneglycol-bis-3(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate,2,6-di-tert-butyl-4-methylphenol,2,2′-methylenebis(4-methyl-6-tert-butylphenol),tri(2,4-di-tert-butylphenyl)phosphite,n-octadecyl-3(3,5-di-tert-butyl-4-hydroxyphenyl)propionate,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,tetrakis(3-(3-3,5-di-tert-butyl-4-hydroxyphenyl)propionate), distearylthiodipropionate, di-phenyl-isooctyl propionate, and the like, withoutbeing limited thereto. These antioxidants may be used alone or incombination thereof.

After completion of polymerization, the aromatic vinyl copolymer may beobtained in particle form through cooling, cleaning, dehydration,drying, and the like.

The aromatic vinyl copolymer may be a branched and/or crosslinkedcopolymer. As used here, the degree of crosslinking of the copolymer maybe identified based on the amount of insolubles as measured by Soxhletextraction. In Soxhlet extraction, an organic solvent selected from thegroup consisting of toluene, tetrahydrofuran, ethyl acetate, chloroform,and mixtures thereof may be used, without being limited thereto. Inexemplary embodiments, tetrahydrofuran (THF) can be used as a solvent.

FIG. 1 shows a Soxhlet extractor according to one embodiment of thepresent invention. Specifically, when a solvent 12 such astetrahydrofuran contained in a container 11 of the reactor is vaporizedusing a heater 13 and the vaporized solvent flows into a condenser 15(which includes a cooling water inlet 16 and a cooling water outlet 17)through a vaporization line 14, the solvent is liquefied again in thecondenser 15 and stored in a storage member which is included in acylindrical filter 18 and contains the copolymer (solid). Next, when theamount of stored solvent is sufficiently increased to allow the solventto be discharged from the storage member, the solvent flows into thecontainer 11 through a circulation line 19 together with solubles of thecopolymer extracted into the solvent. This process is repeated, wherebythe solubles of the copolymer are contained in the container 11 andinsolubles of the copolymer remain in the storage member of thecylindrical filter 18. A weight of the insolubles is measured todetermine the amount of the insolubles in the copolymer.

In exemplary embodiments, the aromatic vinyl copolymer may include about5 wt % to about 100 wt %, for example, about 10 wt % to about 80 wt %,of insolubles remaining after Soxhlet extraction for about 48 hoursusing tetrahydrofuran (THF) based on the total weight of the aromaticvinyl copolymer. Within this range, the copolymer can provide excellentimpact resistance and matting properties.

In exemplary embodiment, the aromatic vinyl copolymer may include about0.03 wt % to about 3.26 wt %, for example, about 0.5 wt % to about 2.5wt %, of silicon as measured by X-ray fluorescence (XRF) analysis.Within this range, the copolymer can provide excellent impact resistanceand matting properties.

As used herein, XRF is fluorescent X-ray spectroscopy which analyzeswavelength distribution of X-rays secondarily emitted from a materialthat has been excited by bombarding with X-rays, thereby estimating thekinds or composition ratio of elements in the material. XRF analysis maybe performed using a typical instrument. In the present invention, anX-ray fluorescence spectrometer (Model: Axios Advanced, Manufacturer:PANalytical) is used. XRF analysis on silicon may be performed, forexample, by a process in which a standard specimen for analysis isprepared, followed by measurement of elemental silicon (Si) included inthe standard specimen by X-ray fluorescence (XRF) analysis and plottinga calibration curve based thereon, and then a specimen of the copolymeraccording to the invention is prepared, followed by measuring elementalsilicon (Si) included in the specimen by X-ray fluorescence (XRF)analysis and substituting the measured values to the calibration curve,thereby performing quantitative analysis.

In exemplary embodiments, the aromatic vinyl copolymer may have a glasstransition temperature of about 95° C. to about 115° C., for example,about 100° C. to about 110° C. Within this range, a thermoplastic resincomposition including the aromatic vinyl copolymer can have excellentinjection moldability.

In accordance with another embodiment, a thermoplastic resin compositionincludes the aromatic vinyl copolymer capable of exhibiting excellentimpact resistance and matting properties as set forth above.

In exemplary embodiments, the thermoplastic resin composition mayinclude the aromatic vinyl copolymer in an amount of about 1 wt % toabout 50 wt %, for example, about 5 wt % to about 30 wt %, and asanother example about 10 wt % to about 25 wt %, based on the totalweight (100 wt %) of the thermoplastic resin composition. In someembodiments, the thermoplastic resin composition may include thearomatic vinyl copolymer in an amount of about 1, 2, 3, 4, 5, 6, 7, 8,9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26,27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44,45, 46, 47, 48, 49, or 50 wt %. Further, according to some embodiments,the amount of the aromatic vinyl copolymer can be in a range from aboutany of the foregoing amounts to about any other of the foregoingamounts.

Within this range, the thermoplastic resin composition can haveexcellent impact resistance and matting properties.

In addition to the aromatic vinyl copolymer, the thermoplastic resincomposition may further include one or more of a typical thermoplasticresin, for example, a rubber-modified aromatic vinyl copolymer resin, apolycarbonate resin, a poly(meth)acrylate resin, or a mixture thereof.

The rubber-modified aromatic vinyl copolymer may include: about 10 wt %to about 100 wt % of (a) a graft copolymer in which an aromatic vinylmonomer and a monomer copolymerizable with the aromatic vinyl monomerare grafted to a rubbery polymer; and optionally about 90 wt % or lessof (b) an aromatic vinyl copolymer in which an aromatic vinyl monomerand a monomer copolymerizable with the aromatic vinyl monomer arecopolymerized. That is, the rubber-modified aromatic vinyl copolymeraccording to the present invention may be prepared using the graftcopolymer (a) alone, or may be prepared using a mixture of the graftcopolymer (a) and the aromatic vinyl copolymer (b).

In exemplary embodiments, the graft copolymer (a) may be polymerized byadding an aromatic vinyl monomer, a monomer copolymerizable with thearomatic vinyl monomer and the like to a rubbery polymer, and thearomatic vinyl copolymer (b) may be polymerized by addition of anaromatic vinyl monomer, a monomer copolymerizable with the aromaticvinyl monomer and the like. As used herein, polymerization may beperformed by any polymerization method known in the art, such asemulsion polymerization, suspension polymerization, and bulkpolymerization. In bulk polymerization, the rubber-modified aromaticvinyl copolymer in which the graft copolymer (a) is dispersed in amatrix, i.e. the aromatic vinyl copolymer (b), may be prepared throughsingle-step reaction without separately preparing the graft copolymer(a) and the aromatic vinyl copolymer (b).

In exemplary embodiments, a rubber (rubbery polymer) may be present inan amount of about 5 wt % to about 50 wt % in the final rubber-modifiedaromatic vinyl copolymer. In addition, the rubber may have a z-averageparticle size of about 0.05 μm to about 6 μm. Within this range, thethermoplastic resin composition can have excellent properties in termsof impact resistance and the like.

Hereinafter, the graft copolymer (a) and the aromatic vinyl copolymer(b) will be described in more detail.

(a) Graft Copolymer

The graft copolymer may be obtained by grafting an aromatic vinylmonomer and a monomer copolymerizable with the aromatic vinyl monomer toa rubbery polymer, and may further optionally include a monomer forimparting processability and heat resistance, as needed.

Examples of the rubbery polymer may include without limitation dienerubbers such as polybutadiene, poly(styrene-butadiene),poly(acrylonitrile-butadiene), and the like; saturated rubbers obtainedby adding hydrogen to the diene rubbers, isoprene rubbers, and the like;acrylic rubbers such as poly(butyl acrylate); ethylene-propylene-dienemonomer terpolymers (EPDM); and the like, and mixtures thereof. Inexemplary embodiments, the rubbery polymer can be a diene rubber, forexample a butadiene rubber.

The rubbery polymer may be present in an amount of about 5 wt % to about65 wt %, for example, about 10 wt % to about 60 wt %, and as anotherexample about 20 wt % to about 50 wt %, based on the total weight (100wt %) of the graft copolymer (a). Within this range, the thermoplasticresin composition can have excellent impact strength and good balancebetween mechanical properties.

The rubbery polymer (rubbery particles) may have an average (z-average)particle size of about 0.05 μm to about 6 μm, for example, about 0.15 μmto about 4 μm, and as another example about 0.25 μm to about 3.5 μm.Within this range, the thermoplastic resin composition can haveexcellent impact strength and external appearance.

The aromatic vinyl monomer is an aromatic vinyl monomer capable of beinggrafted to the rubbery copolymer, and may include, for example, styrene,α-methylstyrene, β-methylstyrene, p-methylstyrene, p-t-butylstyrene,ethylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene,dibromostyrene, vinyl naphthalene, and the like, and mixtures thereof,without being limited thereto. In exemplary embodiments, the aromaticvinyl monomer may include styrene.

The aromatic vinyl monomer may be present in an amount of about 15 wt %to about 94 wt %, for example, about 20 wt % to about 80 wt %, and asanother example about 30 wt % to about 60 wt %, based on the totalweight (100 wt %) of the graft copolymer (a). Within this range, thethermoplastic resin composition can have excellent impact strength andgood balance between mechanical properties.

Examples of the monomer copolymerizable with the aromatic vinyl monomermay include without limitation vinyl cyanide compounds, such asacrylonitrile, ethacrylonitrile, methacrylonitrile, and the like. Thesemonomers may be used alone or in combination thereof.

The monomer copolymerizable with the aromatic vinyl monomer may bepresent in an amount of about 1 wt % to about 50 wt %, for example,about 5 wt % to about 45 wt %, and as another example about 10 wt % toabout 30 wt %, based on the total weight (100 wt %) of the graftcopolymer. Within this range, the thermoplastic resin composition canhave excellent impact strength and good balance between mechanicalproperties.

Examples of the monomer for imparting processability and heat resistancemay include acrylic acid, methacrylic acid, maleic anhydride,N-substituted maleimide, and the like, and mixtures thereof, withoutbeing limited thereto. The monomer for imparting processability and heatresistance is optionally present in an amount of about 15 wt % or less,for example, about 0.1 wt % to about 10 wt %, based on the total weight(100 wt %) of the graft copolymer. Within this range, the monomer canimpart processability and heat resistance to the thermoplastic resincomposition with minimal or no deterioration of other properties.

(b) Aromatic Vinyl Copolymer

The aromatic vinyl copolymer may be prepared using a mixture of themonomers, excluding the rubber (rubbery polymer), of the graft copolymer(a), and the ratio of the monomers may vary depending uponcompatibility. For example, the aromatic vinyl copolymer may be obtainedby copolymerization of the aromatic vinyl monomer and the monomercopolymerizable with the aromatic vinyl monomer.

Examples of the aromatic vinyl monomer may include styrene,α-methylstyrene, β-methylstyrene, p-methylstyrene, p-t-butylstyrene,ethylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene,dibromostyrene, vinyl naphthalene, and the like, and mixtures thereof,without being limited thereto. In exemplary embodiments, the aromaticvinyl monomer may include styrene.

Examples of the monomer copolymerizable with the aromatic vinyl monomermay include without limitation vinyl cyanide compounds, such asacrylonitrile, ethacrylonitrile, methacrylonitrile, and the like. Thesemonomers may be used alone or in combination thereof.

The aromatic vinyl copolymer may further include optionally a monomerfor imparting processability and heat resistance, as needed. Examples ofthe monomer for imparting processability and heat resistance may includeacrylic acid, methacrylic acid, maleic anhydride, N-substitutedmaleimide, and the like, and mixtures thereof, without being limitedthereto.

In the aromatic vinyl copolymer, the aromatic vinyl monomer may bepresent in an amount of about 50 wt % to about 95 wt %, for example,about 60 wt % to about 90 wt %, and as another example about 70 wt % toabout 80 wt %, based on the total weight (100 wt %) of the aromaticvinyl copolymer. Within this range, the thermoplastic resin compositioncan have excellent impact strength and good balance between mechanicalproperties.

The monomer copolymerizable with the aromatic vinyl monomer may bepresent in an amount of about 5 wt % to about 50 wt %, for example,about 10 wt % to about 40 wt %, and as another example about 20 wt % toabout 30 wt %, based on the total weight (100 wt %) of the aromaticvinyl copolymer. Within this range, the thermoplastic resin compositioncan have excellent impact strength and good balance between mechanicalproperties.

In addition, the monomer for imparting processability and heatresistance may be present in an amount of about 30 wt % or less, forexample, about 0.1 wt % to about 20 wt % based on the total weight (100wt %) of the aromatic vinyl copolymer. Within this range, the monomercan impart processability and heat resistance to the thermoplastic resincomposition with minimal or no deterioration of other properties.

The aromatic vinyl copolymer may have a weight average molecular weightof about 50,000 g/mol to about 500,000 g/mol, without being limitedthereto.

Examples of the rubber-modified aromatic vinyl copolymer may includewithout limitation a resin obtained from the graft copolymer (a) alone,such as a copolymer g-ABS obtained by grafting a styrene monomer, whichis an aromatic vinyl compound, and an acrylonitrile monomer, which is avinyl cyanide compound, to a butadiene rubbery polymer core; and/or aresin obtained from a mixture of the graft copolymer (a) and thearomatic vinyl copolymer (b), such as acrylonitrile-butadiene-styrene(ABS) copolymer resins, acrylonitrile-ethylene-propylene rubber-styrene(AES) copolymer resins, and/or acrylonitrile-acrylic rubber-styrene(AAS) copolymer resins. As used here, in the ABS resin, g-ABS, as thegraft copolymer (a), is dispersed in a styrene-acrylonitrile (SAN)copolymer resin as the aromatic vinyl copolymer (b).

Further, the rubber-modified aromatic vinyl copolymer may include atleast two graft copolymers (a), the rubbery polymers (rubber particles)of which have different average (z-average) particle sizes. In thiscase, the thermoplastic resin composition can have further enhancedimpact resistance.

In exemplary embodiments, the thermoplastic resin composition mayinclude the rubber-modified aromatic vinyl copolymer in an amount ofabout 5 wt % to about 99 wt %, for example, about 15 wt % to about 95 wt%, for example, about 30 wt % to about 90 wt %, based on the totalweight (100 wt %) of the thermoplastic resin composition. Within thisrange, the thermoplastic resin composition can exhibit both excellentimpact resistance and matting properties.

The polycarbonate resin may include any typical thermoplasticpolycarbonate resins without limitation. For example, the polycarbonateresin may be an aromatic polycarbonate resin prepared by reacting acarbonate precursor, such as phosgene, halogen formate, or carbonatediester with one or more diphenols (aromatic dihydroxy compounds).

Examples of the diphenols may include 4,4′-biphenol,2,2-bis-(4-hydroxyphenyl)-propane,2,4-bis-(4-hydroxyphenyl)-2-methylbutane,1,1-bis-(4-hydroxyphenyl)-cyclohexane,2,2-bis-(3-chloro-4-hydroxyphenyl)-propane,2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane, and the like andmixtures thereof, without being limited thereto. For example, thediphenol may include 2,2-bis-(4-hydroxyphenyl)-propane,2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane, and/or1,1-bis-(4-hydroxyphenyl)-cyclohexane, for example2,2-bis-(4-hydroxyphenyl)-propane, which is also referred to asbisphenol A.

The polycarbonate resin may include a branched polycarbonate resin, andmay also be prepared by adding about 0.05 mol % to about 2 mol % of apolyfunctional compound containing tri- or higher functional groups, forexample, tri- or higher-valent phenol groups, based on the total amountof the diphenols used in polymerization. The polycarbonate resin may beused in the form of a homo-polycarbonate resin, a co-polycarbonateresin, or a blend thereof. In addition, the polycarbonate resin may bepartially or completely replaced by an aromatic polyester-carbonateresin obtained by polymerization in the presence of an ester precursor,for example, a bifunctional carboxylic acid.

In exemplary embodiments, the polycarbonate resin may have a weightaverage molecular weight (Mw) of about 10,000 g/mol to about 200,000g/mol, for example, about 15,000 g/mol to about 120,000 g/mol.

In exemplary embodiments, the thermoplastic resin composition mayinclude the polycarbonate resin in an amount of about 80 wt % or less,for example, about 70 wt % or less, and as another example about 60 wt %or less, based on the total weight (100 wt %) of the thermoplastic resincomposition. Within this range, the thermoplastic resin composition canhave both excellent impact resistance and matting properties.

The poly(meth)acrylate resin may include any typical poly(meth)acrylateresins without limitation. For example, the poly(meth)acrylate resin maybe polymethylmethacrylate (PMMA), without being limited thereto.

In exemplary embodiments, the poly(meth)acrylate resin may have a weightaverage molecular weight (Mw) of about 10,000 g/mol to about 200,000g/mol, for example, about 15,000 g/mol to about 120,000 g/mol.

In exemplary embodiments, the thermoplastic resin composition mayinclude the poly(meth)acrylate resin in an amount of about 20 wt % orless, for example, about 15 wt % or less, based on the total weight (100wt %) of the thermoplastic resin composition. Within this range, thethermoplastic resin composition can have both excellent impactresistance and matting properties.

Examples of the thermoplastic resin that can be present in thethermoplastic resin composition can include styrene-acrylonitrilecopolymer (SAN) resin, methyl methacrylate-styrene-acrylonitrilecopolymer (MSAN) resin, acrylonitrile-butadiene-styrene copolymer (ABS)resin, methyl methacrylate-acrylonitrile-butadiene-styrene copolymer(MABS) resin, acrylonitrile-styrene-acrylate copolymer (ASA) resin,polycarbonate (PC)/acrylonitrile-butadiene-styrene copolymer (ABS)alloy, polycarbonate (PC)/acrylonitrile-styrene-acrylate copolymer (ASA)alloy, polymethylmethacrylate (PMMA)/acrylonitrile-butadiene-styrenecopolymer (ABS) alloy, polymethylmethacrylate (PMMA)/methylmethacrylate-acrylonitrile-butadiene-styrene copolymer (MABS) alloy,polymethylmethacrylate (PMMA)/acrylonitrile-styrene-acrylate copolymer(ASA) alloy, and the like, and mixtures thereof, without being limitedthereto.

The thermoplastic resin composition according to the present inventionmay further include one or more typical additives, as needed. Examplesof the additives may include without limitation flame retardants,antioxidants, anti-dripping agents, lubricants, release agents,nucleating agents, antistatic agents, stabilizers, pigments, dyes, andthe like, and mixtures thereof. When the additives are used, theadditives may be present in an amount of 0.001 wt % to 10 wt % based onthe total weight (100 wt %) of the thermoplastic resin composition,without being limited thereto.

The thermoplastic resin composition according to the present inventioncan exhibit excellent impact resistance and matting properties, and mayhave: a gloss of about 20% to about 55%, for example, about 20% to about50% as measured at an angle of about 60° in accordance with ASTM D523;and an Izod impact strength of about 10 kgf·cm/cm to about 30 kgf·cm/cm,for example, about 15 kgf·cm/cm to about 25 kgf·cm/cm as measured on anabout ⅛″ thick specimen in accordance with ASTM D256.

In accordance with another embodiment, a molded article is formed of thethermoplastic resin composition as set forth above. The thermoplasticresin composition according to the present invention may be prepared bya method of preparing a thermoplastic resin composition known in theart. For example, the above components and, optionally, one or moreadditives can be mixed, followed by melt extrusion in an extruder,thereby preparing a resin composition in the form of pellets. Theprepared pellets may be produced into various molded articles (products)through various molding methods, such as injection molding, extrusion,vacuum molding, casting, and the like. Such molding methods are wellknown to those skilled in the art. The thermoplastic resin compositioncan exhibit excellent flowability (moldability), thereby allowing easyinjection molding. The molded article can be a low gloss product havinga luxurious appearance, and may be useful for interior/exteriormaterials for automobiles or electric/electronic products and exteriormaterials for construction.

Hereinafter, the present invention will be described in more detail withreference to the following examples. It should be understood that theseexamples are provided for illustration only and are not to be construedin any way as limiting the present invention.

EXAMPLE Preparative Example 1: Preparation of Aromatic Vinyl Copolymer

A reaction mixture including: a monomer mixture including 76 wt % ofstyrene and 24 wt % of acrylonitrile; 2 parts by weight of1,3,5,7-tetramethyl-1,3,5,7-tetravinyl-cyclotetrasiloxane (weightaverage molecular weight: 344.7 g/mol); and 0.5 parts by weight ofmethacrylated polydimethylsiloxane (MPDMS) having a weight averagemolecular weight of 9,000 g/mol, based on 100 parts by weight of themonomer mixture, is prepared. Then, based on 100 parts by weight of thereaction mixture, 0.2 parts by weight of t-dodecyl mercaptan (TDM) as achain transfer agent and 0.2 parts by weight of azobisisobutyronitrile(AIBN) as a polymerization initiator are added to the reaction mixture,which in turn is introduced into an aqueous solution in which asuspension stabilizer is dissolved (the aqueous solution including 0.5parts by weight of the suspension stabilizer (tricalcium phosphate) and140 parts by weight of deionized water). Next, suspension polymerizationis performed at 75° C. for 5 hours, thereby preparing an aromatic vinylcopolymer.

Preparative Example 2: Preparation of Aromatic Vinyl Copolymer

An aromatic vinyl copolymer is prepared through suspensionpolymerization in the same manner as in Preparative Example 1 exceptthat 1 part by weight of methacrylated polydimethylsiloxane (MPDMS) isused.

Preparative Example 3: Preparation of Aromatic Vinyl Copolymer

An aromatic vinyl copolymer is prepared through suspensionpolymerization in the same manner as in Preparative Example 1 exceptthat 3 parts by weight of methacrylated polydimethylsiloxane (MPDMS) isused.

Preparative Example 4: Preparation of Aromatic Vinyl Copolymer

An aromatic vinyl copolymer is prepared through suspensionpolymerization in the same manner as in Preparative Example 1 exceptthat 1,3,5,7-tetramethyl-1,3,5,7-tetravinyl-cyclotetrasiloxane is notused.

Property Evaluation

(1) Glass transition temperature (Tg, unit: ° C.): Using a calorimeter(Q2910, TA Instruments), the prepared specimen is heated to 160° C. at arate of 20° C./min and then slowly cooled to 50° C. to maintainequilibrium, followed by heating to 160° C. at a rate of 10° C./min. Aninflection point on an obtained endothermic transition curve isdetermined as a glass transition temperature.

(2) Amount of insolubles in copolymer upon Soxhlet extraction (unit: wt%): The copolymer is subjected to Soxhlet extraction for 48 hours usingtetrahydrofuran, followed by measuring an amount of insolubles remainingin the copolymer after extraction.

(3) Amount of silicon in copolymer (unit: wt %): Using a X-rayfluorescence spectrometer (Model: Axios Advanced, Manufacturer:PANalytical, Netherlands), a standard specimen for analysis is prepared,followed by measurement of elemental silicon (Si) included in thestandard specimen by X-ray fluorescence (XRF) analysis and plotting acalibration curve based thereon. Then, a specimen of the copolymer isprepared, followed by measuring elemental silicon (Si) included in thespecimen by X-ray fluorescence (XRF) analysis and substituting themeasured values to the calibration curve, thereby performingquantitative analysis.

TABLE 1 Prepar- ative Preparative Preparative Preparative Example 1Example 2 Example 3 Example 4 Glass transition 102.1 102.2 101.8 102.0temperature (° C.) Amount of 43.3 44.2 45.3 3.3 insolubles (wt %) Amountof 1.20 1.39 2.12 1.10 silicon (wt %)

Details of components used in Examples and Comparative Examples are asfollows.

(A) Graft copolymer

(A1) A core-shell type graft copolymer (average (z-average) particlesize of rubber: 320 nm) prepared by grafting 60 parts by weight of abutyl acrylate rubber and 40 parts by weight of a monomer mixtureincluding 67 wt % of styrene and 33 wt % of acrylonitrile is used.

(A2) A core-shell type graft copolymer (average (z-average) particlesize of rubber: 200 nm) prepared by grafting 50 parts by weight of abutyl acrylate rubber and 50 parts by weight of a monomer mixtureincluding 67 wt % of styrene and 33 wt % of acrylonitrile is used.

(B) Aromatic vinyl copolymer

An aromatic vinyl copolymer (SAN), which was prepared by suspensionpolymerization of a monomer mixture including 76 wt % of styrene and 24wt % of acrylonitrile and had a weight average molecular weight of100,000 g/mol, is used.

(C) Aromatic vinyl copolymer

(C1) An aromatic vinyl copolymer of Preparative Example 1 is used.

(C2) An aromatic vinyl copolymer of Preparative Example 2 is used.

(C3) An aromatic vinyl copolymer of Preparative Example 3 is used.

(C4) An aromatic vinyl copolymer of Preparative Example 4 is used.

Examples 1 to 3 and Comparative Example 1

According to compositions and amounts as listed in Table 2, thecomponents are mixed for 10 minutes using a tumbler mixer and thenintroduced into a 44 L/D twin-screw type extruder having a diameter of45 mm, followed by melting and extrusion at a barrel temperature of 250°C. and stirring rate of 250 rpm, thereby preparing pellets. The preparedpellets are dried at 80° C. for 2 hours or more, followed by injectionmolding using an injection molding machine (LGH-140N, LG Cable Co.,Ltd.) at a cylinder temperature of 230° C., thereby preparing aspecimen. The prepared specimen is evaluated as to the followingproperties. Results are shown in Table 2.

Property Evaluation

(1) Gloss (surface gloss) (unit: %): Gloss is measured at an angle of60° in accordance with ASTM D523 using a BYK-Gardner gloss meter (BYKCo., Ltd.).

(2) Izod impact strength (unit: kgf·cm/cm): Izod impact strength ismeasured on a ⅛″ thick notched Izod specimen in accordance with ASTMD256.

TABLE 2 Example Comparative Example 1 2 3 1 (A1) (wt %) 28 28 28 28 (A2)(wt %) 10 10 10 10 (B) (wt %) 43 43 43 43 (C1) (wt %) 19 — — — (C2) (wt%) — 19 — — (C3) (wt %) — — 19 — (C4) (wt %) — — — 19 Gloss 28 28 29 57Izod impact strength 21.0 21.1 17.8 20.7

From the results of Table 2, it could be seen that the thermoplasticresin compositions including the aromatic vinyl copolymers according tothe present invention exhibit excellent impact resistance, gloss, andthe like.

On the other hand, it could be seen that the thermoplastic resincomposition (Comparative Example 1) including the aromatic vinylcopolymer, in which only the second silicone compound is copolymerized,exhibits significant deterioration in gloss.

Although some embodiments have been described herein, it should beunderstood that these embodiments are provided for illustration only andare not to be construed in any way as limiting the present invention,and that various modifications, changes, alterations, and equivalentembodiments can be made by those skilled in the art without departingfrom the spirit and scope of the invention. Therefore, the scope of thepresent invention should be defined by the appended claims andequivalents thereof.

What is claimed is:
 1. A thermoplastic resin composition comprising anaromatic vinyl copolymer, wherein the aromatic vinyl copolymercomprises: an aromatic vinyl compound; a vinyl cyanide compound; a firstsilicone compound having a weight average molecular weight of about 150g/mol to about 3,000 g/mol and comprising at least two unsaturatedreactive groups; and a second silicone compound having a weight averagemolecular weight of about 6,500 g/mol to about 30,000 g/mol andcomprising at least two unsaturated reactive groups, wherein thearomatic vinyl copolymer has a glass transition temperature of about 95°C. to about 115° C., and wherein the thermoplastic resin compositionhas: a gloss of about 20% to about 55% as measured at an angle of about60° in accordance with ASTM D523; and an Izod impact strength of about10 kgf·cm/cm to about 30 kgf·cm/cm as measured on an about ⅛″ thickspecimen in accordance with ASTM D256.
 2. The thermoplastic resincomposition according to claim 1, comprising the aromatic vinylcopolymer in an amount of about 1 wt % to about 50 wt % based on thetotal weight of the thermoplastic resin composition.
 3. Thethermoplastic resin composition according to claim 1, comprising: athermoplastic resin comprising at least one of a rubber-modifiedaromatic copolymer, a polycarbonate resin, and a poly(meth)acrylateresin.
 4. A molded article formed of the thermoplastic resin compositionaccording to claim
 1. 5. The thermoplastic resin composition accordingto claim 1, wherein the aromatic vinyl copolymer consists of thearomatic vinyl compound, the vinyl cyanide compound, the first siliconecompound having a weight average molecular weight of about 150 g/mol toabout 3,000 g/mol and comprising at least two unsaturated reactivegroups, and the second silicone compound having a weight averagemolecular weight of about 6,500 g/mol to about 30,000 g/mol andcomprising at least two unsaturated reactive groups.
 6. Thethermoplastic resin composition according to claim 1, wherein thearomatic vinyl copolymer comprises: about 0.05 parts by weight to about10 parts by weight of the first silicone compound; and about 0.05 partsby weight to about 10 parts by weight of the second silicone compound,each based on about 100 parts by weight of a monomer mixture comprisingabout 60 wt % to about 80 wt % of the aromatic vinyl compound and about20 wt % to about 40 wt % of the vinyl cyanide compound.
 7. Thethermoplastic resin composition according to claim 1, wherein the firstsilicone compound is a compound represented by Formula 1 and the secondsilicone compound is a compound represented by Formula 2:

wherein a, b and c are the same or different and are each independentlyan integer of 0 to 79, provided that a, b and c are not 0 at the sametime, and a+b+c ranges from 1 to 79; R₁ to R₈ are the same or differentand are each independently a hydrogen atom, a substituted orunsubstituted C₁ to C₃₀ alkyl group, a substituted or unsubstituted C₂to C₃₀ alkenyl group, a substituted or unsubstituted C₂ to C₃₀ alkynylgroup, a substituted or unsubstituted C₃ to C₃₀ cycloalkyl group, asubstituted or unsubstituted C₆ to C₃₀ aryl group, a substituted orunsubstituted C₁ to C₃₀ heteroaryl group, a (meth)acrylate group, ahydroxyl group, an alkoxy group, an amino group, an epoxy group, acarboxyl group, a halogen group, an ester group, an isocyanate group, ora mercapto group; with the proviso that at least two of R₁ to R₈ includepolymerizable unsaturated reactive groups; wherein the compound has alinear structure or a cyclic structure in which R₁ and R₈ are linked toeach other or form a single bond;

wherein d, e and f are the same or different and are each independentlyan integer of 0 to 1,500, with the proviso that d, e and f are not 0 atthe same time, and d+e+f ranges from 80 to 1,500; R₉ to R₁₆ are the sameor different and are each independently a hydrogen atom, a substitutedor unsubstituted C₁ to C₃₀ alkyl group, a substituted or unsubstitutedC₂ to C₃₀ alkenyl group, a substituted or unsubstituted C₂ to C₃₀alkynyl group, a substituted or unsubstituted C₃ to C₃₀ cycloalkylgroup, a substituted or unsubstituted C₆ to C₃₀ aryl group, asubstituted or unsubstituted C₁ to C₃₀ heteroaryl group, a(meth)acrylate group, a hydroxyl group, an alkoxy group, an amino group,an epoxy group, a carboxyl group, a halogen group, an ester group, anisocyanate group, or a mercapto group; with the proviso that at leasttwo of R₉ to R₁₆ include polymerizable unsaturated reactive groups. 8.The thermoplastic resin composition according to claim 7, wherein thecompound represented by Formula 1 comprises a compound represented byFormula 3:

wherein R₁₇ to R₂₂ are the same or different and are each independentlya hydrogen atom, a substituted or unsubstituted C₁ to C₂₀ alkyl group, asubstituted or unsubstituted C₂ to C₂₀ alkenyl group, or a substitutedor unsubstituted C₆ to C₂₀ aryl group; R₂₃ to R₂₅ are the same ordifferent and are each independently a hydrogen atom or a substituted orunsubstituted C₁ to C₆ alkyl group; and n is an integer of 1 to
 6. 9.The thermoplastic resin composition according to claim 1, wherein adifference in weight average molecular weight between the first siliconecompound and the second silicone compound ranges from about 5,000 g/molto about 20,000 g/mol.
 10. The thermoplastic resin composition accordingto claim 1, wherein the aromatic vinyl copolymer comprises about 5 wt %to about 100 wt % of insolubles remaining after Soxhlet extraction forabout 48 hours using tetrahydrofuran (THF) based on the total weight ofthe aromatic vinyl copolymer.
 11. The thermoplastic resin compositionaccording to claim 1, wherein the aromatic vinyl copolymer comprisesabout 0.03 wt % to about 3.26 wt % of silicon as measured by X-rayfluorescence (XRF) analysis based on the total weight of the aromaticvinyl copolymer.